JP6513722B2 - Aromatic polyamide film for transparent flexible substrates - Google Patents

Description

  This application is related to US Provisional Patent Application No. 61 / 466,751, entitled "Aromatic polyamide film for transparent flexible substrates", filed March 23, 2011, the contents of which are incorporated herein by reference. Claim the priority of

  The present invention relates to the production of thermally and dimensionally stable transparent polymeric films. More specifically, the present invention is directed to the preparation and use of aromatic polyamides having a rigid framework with a glass transition temperature above 300 ° C., but which can still be dissolved in conventional organic solvents without the need for the presence of inorganic salts. About. These polymer films can be prepared by solution casting and cured at elevated temperatures. The cured films exhibit high light transmission (transmission> 80%), low thermal expansion coefficient (CTE <20 ppm / ° C.), and good solvent resistance over the range of 400-750 nm.

  Organic light emitting diode (OLED) displays are $ 1.25 billion in 2010 and are expected to grow at a 25% annual rate. OLED displays are a good alternative to liquid crystal displays (LCDs) in the cellular phone display, digital camera and global positioning system (GPS) market segments due to their high efficiency and high contrast ratio. It has become. In these applications, high electrical efficiency, small size and robustness are emphasized. This has increased the demand for active matrix OLEDs (AMOLEDs) that consume less power, have faster response times, and have higher resolution. As AMOLED innovations improve these properties, adoption of AMOLEDs in portable devices will further accelerate and the range of devices that use AMOLEDs will expand. These performance factors are mainly driven by the processing temperature of the electronic device. The AMOLED has a thin film transistor (TFT) array structure deposited on a transparent substrate. Raising the TFT deposition temperature allows a dramatic improvement in the electrical efficiency of the display. At present, glass plates are used as AMOLED substrates. Glass plates provide high processing temperatures (> 500 ° C.) and good barrier properties, but because they are relatively thick, heavy, hard and fragile, product design freedom and display robustness are reduced. Thus, there is a need for lighter, thinner and more robust alternatives from mobile device manufacturers. Flexible substrate materials will also open up new possibilities for product design and enable lower cost roll-to-roll manufacturing.

Many polymeric thin films have excellent flexibility, permeability, and are relatively inexpensive and lightweight. Polymeric films are excellent candidates for substrates for flexible electronics, including flexible displays and flexible solar panels currently under development. Compared to rigid substrates such as glass, flexible substrates offer several significant potential advantages in electronic devices, including:
a. Lightweight (glass substrates occupy about 98% of the total weight in thin film solar cells).
b. Flexible (easy to handle, low shipping costs, and / or have more applications for both raw materials and products).
c. Because it is suitable for roll-to-roll manufacturing, the manufacturing cost may be significantly reduced.

In order to make these advantages inherent in polymer substrates accessible for flexible display applications, several issues must be addressed, including:
a. Enhance thermal stability;
b. Reduce the coefficient of thermal expansion (CTE);
c. Maintain high permeability during high temperature processing; and d. Improve oxygen and water vapor barrier properties. At present, there are no pure polymeric films that can provide sufficient barrier properties. Additional barrier layers must be applied to achieve the target barrier properties.

  Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), cyclic olefin polymer (COP), polyarylates (PAR), polyimides (PI) and others, Several polymeric films have been evaluated as transparent flexible substrates. However, no single film can meet all the requirements. At present, the industry standard for this application is PEN film, which meets some of the requirements (> 80% transmission between 400 nm and 750 nm, CTE <20 ppm / ° C), but with a working temperature Limited (<200 ° C). Transparent polymeric films with higher thermal stability (Tg> 300 ° C.) and lower CTE (<20 ppm / ° C.) are desired.

  While conventional aromatic polyimides are well known to have excellent thermal and mechanical properties, their films must be cast from their polyamic acid precursors and are usually dark. Yellow to orange. While some aromatic polyimides have been prepared that can be solution cast to form colorless films in the visible region, such films do not exhibit the required low CTE (e.g. Li.F.W.Harris and S.Z.D.Cheng, Polymer, 37, 23, 5321 (1996)). These films are also not solvent resistant. Patents of JP-A 2007-063417 and JP-A 2007-231224 and A. S. Polyimide films based in part or in whole on alicyclic monomers, such as those described in the publication by Matthews et al. (J. Appl. Polym. Sci., 102, 3316-3326, 2006) , Show improved permeability. The Tg of these polymers can exceed 300 ° C., but at these temperatures they do not exhibit sufficient thermal stability due to aliphatic units.

  H. Fiber reinforced polymer composite films, such as those reported by Ito (Jap. J. Appl. Phys., 45, No. 5B, p. 4325, 2006), have the dimensional characteristics of fiber glass in polymer films. Combining stability provides an alternative way to achieve low CTE. However, in order to maintain high transparency, the refractive index of the matrix polymer and the refractive index of the fiber must be precisely matched, which greatly limits the choice of matrix polymer in the organosilicon resin. The effect of lowering the CTE is not remarkable by using nanoparticles as a filler (JM Liu et al., J. SID, vol. 19, No. 1, 2011).

  Most aromatic polyamides have poor solubility in organic solvents and can not be solution cast to form films, but few polymers are prepared that are soluble in polar aprotic solvents containing inorganic salts . Some of these were investigated for use as flexible substrates. For example, JP 2009-79210 A is prepared from fluorine-containing aromatic polyamides and has very low CTE (<0 ppm / ° C.), good permeability (T%> 80 at 450-700 nm) and excellent mechanical It describes a thin film that exhibits properties. However, the maximum thickness of the film made from this polymer is 20 μm, since the preparation of the film must use a dry-wet process in which desalting takes place. Most importantly, this film also has poor resistance to strong organic solvents.

  The present invention relates to transparent films prepared from aromatic copolyamides having a CTE less than 20 ppm / ° C. and a Tg greater than 300 ° C. These films are cast using polyamide solutions in N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) or other polar solvents. The present invention can be prepared in the absence of inorganic salts. Surprisingly, it has been discovered that incorporation of a small number of free pendant carboxyl groups along the polyamide backbone causes the film to be thermally cured at high temperatures, significantly improving the film's solvent resistance.

  According to one aspect of the present invention, there is provided a process for producing a thermally and dimensionally stable transparent aromatic copolyamide film comprising the following steps: (A) of two or more aromatic diamines At least one of the diamines contains one or more free carboxylic acid groups so that the mixture is formed and the amount of carboxylic acid-containing diamine is greater than about 1 mole% and less than about 10 mole% of the total diamine mixture. (B) dissolving the aromatic diamine mixture in a polar solvent; (C) reacting the diamine mixture with at least one aromatic diacid dichloride, hydrochloric acid and a polyamide solution (D) removing the hydrochloric acid using a reagent; (E) casting the polyamide solution to form a film; and (F) Curing the beam at a constant temperature (although the temperature is at least 90% of the glass transition temperature of the film). The curing process involves heating a polymer film containing free acid groups near Tg for several minutes under an inert atmosphere or under reduced pressure. After the curing process, the film resists dissolution and / or swelling in commonly used organic solvents, including NMP, DMAc, dimethylsulfoxide (DMSO) and the like. The term "removing" is defined as meaning physically capturing, neutralizing and / or reacting chemically the hydrochloric acid.

上記の式中、ｎ＝１〜４（制限なしに、１、２、３および４を含む）であり、Ａｒ_１は、芳香族ジカルボン酸塩化物を形成する以下の芳香族単位の群から選択される：

上記の式中、ｐ＝４、ｑ＝３であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は、水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、ハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリールまたはハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_１はそれぞれ異なってもよく、Ｒ_２はそれぞれ異なってもよく、Ｒ_３はそれぞれ異なってもよく、Ｒ_４はそれぞれ異なってもよく、Ｒ_５はそれぞれ異なってもよいことを理解されるべきである。Ｇ_１は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ_２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である。Ａｒ_２は、ジアミンを形成する以下の芳香族単位の群から選択される：

上記の式中、ｐ＝４であり、Ｒ_６、Ｒ_７、Ｒ_８は、水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、ハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリール、ハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_６はそれぞれ異なってもよく、Ｒ_７はそれぞれ異なってもよく、Ｒ_８はそれぞれ異なってもよいことを理解されるべきである。Ｇ_２は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ_２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である。Ａｒ_３は、遊離カルボキシル基を含有するジアミンを形成する以下の芳香族単位の群から選択される：

上記の式中、ｔ＝１〜３であり、Ｒ_９、Ｒ_１０、Ｒ_１１は水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、トリフルオメチルのようなハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリール、ハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_９はそれぞれ異なってもよく、Ｒ_１０はそれぞれ異なってもよく、Ｒ_１１はそれぞれ異なってもよいことを理解されるべきである。Ｇ_３は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である。コポリマーは（Ｉ）および（ＩＩ）の構造を有する複数の繰り返し単位を含有してもよく、その構造中、Ａｒ_１、Ａｒ_２およびＡｒ_３は同一であっても、異なってもよいことを理解されるべきである。 According to another aspect of the invention, transparent aromatic copolyamide films are produced having at least two repeating units of the general formulas (I) and (II) below:

In the above formula, n = 1 to 4 (without limitation, 1, 2, 3 and 4), and Ar ₁ is selected from the group of aromatic units forming aromatic dicarboxylic acid chloride: Will be:

In the above formula, p = 4 and q = 3, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen, halogen (fluorine, chlorine, bromine and iodine), alkyl, halogenated alkyl etc. It is selected from the group consisting of: substituted alkyl of nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, substituted aryl such as aryl or halogenated aryl, alkyl ester and substituted alkyl ester and combinations thereof. It should be understood that R ₁ may be different, R ₂ may be different, R ₃ may be different, R ₄ may be different, and R ₅ may be different. It is. G ₁ is a covalent bond; CH ₂ group; C (CH ₃ ) ₂ group; C (CF ₃ ) ₂ group; C (CX ₃ ) ₂ group selected from the group consisting of X, halogen: CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, perfluorobiphenyl group 9,9-bisphenyl fluorene groups, and substituted aryl groups such as substituted 9,9-bisphenyl fluorenes. Ar ₂ is selected from the following group of aromatic units forming a diamine:

In the above formula, p = 4, and R ₆ , R ₇ and R ₈ are hydrogen, halogen (fluorine, chlorine, bromine and iodine), alkyl, substituted alkyl such as alkyl halide, nitro, cyano, thioalkyl, It is selected from the group consisting of alkoxy, substituted alkoxy such as halogenated alkoxy, aryl, substituted aryl such as halogenated aryl, alkyl ester and substituted alkyl ester and combinations thereof. It is to be understood that R ₆ may be different, R ₇ may be different, and R ₈ may be different. G ₂ is selected from the group consisting of covalent bonds; CH ₂ groups; C (CH ₃ ) ₂ groups; C (CF ₃ ) ₂ groups; C (CX ₃ ) ₂ groups, X is a halogen; CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, perfluorobiphenyl group 9,9-bisphenyl fluorene groups, and substituted aryl groups such as substituted 9,9-bisphenyl fluorenes. Ar ₃ is selected from the following group of aromatic units forming diamines containing free carboxyl groups:

In the above formula, t = 1 to 3, R ₉ , R ₁₀ and R ₁₁ are hydrogen, halogen (fluorine, chlorine, bromine and iodine), alkyl, substituted alkyl such as halogenated alkyl such as trifluoromethyl, It is selected from the group consisting of nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, aryl, substituted aryl such as halogenated aryl, alkyl ester and substituted alkyl ester and combinations thereof. It should be understood that R ₉ may be different, R ₁₀ may be different, and R ₁₁ may be different. G ₃ are covalent bonds; is selected from the group consisting of C _{(CX 3) 2} group, X is a halogen;; CH ₂ group; C _{(CH 3) 2} group; C _{(CF 3) 2} group CO group; O atom; S atoms; SO2 group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, perfluorobiphenyl group, 9,9-bisphenyl fluorene groups and substituted aryl groups such as substituted 9,9-bisphenyl fluorenes. The copolymer may contain a plurality of repeating units having the structures (I) and (II) in which it is understood that Ar ₁ , Ar ₂ and Ar ₃ may be identical or different. It should be.

上記の式中、ｎ＝１〜４（制限なしに、１、２、３および４を含む）であり、Ａｒは、遊離カルボキシル基を含有するジアミンを形成する以下の芳香族単位の群から選択される：

上記の式中、ｍ＝１または２であり、ｔ＝１〜３であり、Ｒ_９、Ｒ_１０、Ｒ_１１は、水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、ハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリールまたはハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_９はそれぞれ異なってもよく、Ｒ_１０はそれぞれ異なってもよく、Ｒ_１１はそれぞれ異なってもよいことを理解されるべきである。Ｇ_３は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ_２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である；
（Ｂ）得られるコポリアミドを溶液流延して、フィルムを形成すること；および
（Ｃ）フィルムを硬化させて、耐溶剤性を誘導すること。 According to yet another embodiment of the present invention, there is provided a method for preparing a transparent film having a CTE less than 20 ppm / ° C. and stable at 300 ° C. for at least 1 hour, comprising the following steps:
(A) A mixture of aromatic diamines, wherein at least one of the diamines contains a pendant carboxyl group of the following general formula (III), is reacted with an aromatic dicarboxylic acid chloride in a polar solvent to contain a pendant carboxyl group Producing copolyamide:

In the above formula, n = 1 to 4 (without limitation including 1, 2, 3 and 4) and Ar is selected from the following group of aromatic units forming diamines containing free carboxyl groups: Will be:

In the above formula, m is 1 or 2, t is 1 to 3, and R ₉ , R ₁₀ and R ₁₁ are hydrogen, halogen (fluorine, chlorine, bromine and iodine), alkyl, halogenated alkyl and the like It is selected from the group consisting of: substituted alkyl of nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, substituted aryl such as aryl or halogenated aryl, alkyl ester and substituted alkyl ester and combinations thereof. It should be understood that R ₉ may be different, R ₁₀ may be different, and R ₁₁ may be different. G ₃ are covalent bonds; is selected from the group consisting of C _{(CX 3) 2} group, X is a halogen;; CH ₂ group; C _{(CH 3) 2} group; C _{(CF 3) 2} group CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, perfluorobiphenyl group A 9,9-bisphenyl fluorene group, and a substituted aryl group such as a substituted 9,9-bisphenyl fluorene;
(B) solution casting the resulting copolyamide to form a film; and (C) curing the film to induce solvent resistance.

  Polyamides containing free pendant carboxyl groups have been prepared using 3,5-diaminobenzoic acid (DAB) or 4,4'-diaminodiphenic acid (DADP). U.S. Pat. No. 5,160,619 describes polyamides containing small amounts of DAB (less than 1 mole%) useful for reverse osmosis films. U.S. Pat. No. 5,039,785 describes polyamides containing more than 10 mole percent DADP useful for high performance fibers. However, no attempt has been made to crosslink by heating films of these polymers to temperatures near their Tg. Even if we tried to crosslink them in this unexpected form, in the case of polymers containing DAB, the carboxylic acid content would be too low to cause crosslinking, and in the case of DADP polymers, Because the degree of crosslinking was too high, the film would be extremely brittle and would not be suitable for flexible substrates.

  Thus, when the copolyamides of the present invention are mixed with about 1 mole% to about 10 mole% of diamines containing free carboxyl groups, when the films of the polymer are heated at temperatures near their Tg, short It was surprising that it was revealed that the polymers were crosslinked within the time (minutes). For example, incorporation of such amounts of DADP or DAB resulted in films resistant to solvents commonly used in the microelectronics industry, which maintain their respective clarity during the crosslinking process. The crosslinked films exhibited high glass transition temperatures (Tg> 300 ° C.) and low thermal expansion coefficients (<20 ppm / ° C.). Thus, the cross-linked film can be used as a flexible substrate to enable the high temperature fabrication of thin film transistors needed for a wide range of microelectronic applications, in particular highly durable or flexible organic light emitting diode (OLED) displays . None of the available materials exhibit all these properties.

  The polymer substrate film of the present invention extends the use of AMOLEDs in portable devices by improving the electrical efficiency of the device and the robustness experienced by the display consumer. In addition to the standard OLED display market, the substrate of the present invention will also enable the development of the flexible display market. These displays can be used for garments, flexible electronic paper and e-book displays, displays for smart cards and flexible displays that can be incorporated into many other new applications. For example, the polymer substrate films of the present invention can be used in flexible sensors. The new devices made from the polymer substrate films of the present invention can dramatically impact everyday life by reducing cost and increasing information accessibility and portability.

  In addition, the polymers of the present invention can be prepared in common organic solvents at room temperature (about 15 ° C. to about 25 ° C.). These polymers can be produced in the absence of inorganic salts. The resulting colorless homogeneous polymer solution can be used directly for subsequent casting. No special polymerization reactors or polymer isolation procedures are required. However, when the polymers are heated for several minutes at temperatures near their Tg, the polymer films are essentially insoluble and chemically resistant to expansion when exposed to inorganic or organic solvents. Thus, this process is suitable for scaling up to metric tons.

   The polymers of the present invention are soluble in polar aprotic solvents without the need for the presence of inorganic salts. These polymers can be solution cast in a batch process or cast directly from the polymerization mixture directly and cured using a roll-tool method to obtain free-standing transparent films with a thickness of more than 20 μm. It is possible to produce. Alternatively, the polymer solution can be solution cast onto a thin glass or reinforced substrate such as a microelectronic device and cured to form a film less than 20 μm thick. These films have high Tg (> 300 ° C.), low CTE (<20 ppm / ° C.), high permeability (T> 80% at 400-750 nm), excellent mechanical properties (tensile strength >> 200 MPa) and low It exhibits hygroscopicity (<2% at room temperature and 100% humidity). Furthermore, these films exhibit excellent chemical resistance after being heated at a temperature of at least 90% of their Tg for a short period of time.

上記の式中、ｐ＝４、ｑ＝３であり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は、水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、ハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリールまたはハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_１はそれぞれ異なってもよく、Ｒ_２はそれぞれ異なってもよく、Ｒ_３はそれぞれ異なってもよく、Ｒ_４はそれぞれ異なってもよく、Ｒ_５はそれぞれ異なってもよいことを理解されるべきである。Ｇ_１は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ_２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である。 Copolyamides were prepared by polymerizing one or more aromatic diacid dichlorides represented by the following general structure:

In the above formula, p = 4 and q = 3, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen, halogen (fluorine, chlorine, bromine and iodine), alkyl, halogenated alkyl etc. It is selected from the group consisting of: substituted alkyl of nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, substituted aryl such as aryl or halogenated aryl, alkyl ester and substituted alkyl ester and combinations thereof. It should be understood that R ₁ may be different, R ₂ may be different, R ₃ may be different, R ₄ may be different, and R ₅ may be different. It is. G ₁ is a covalent bond; CH ₂ group; C (CH ₃ ) ₂ group; C (CF ₃ ) ₂ group; C (CX ₃ ) ₂ group selected from the group consisting of X, halogen: CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, perfluorobiphenyl group 9,9-bisphenyl fluorene groups, and substituted aryl groups such as substituted 9,9-bisphenyl fluorenes.

上記の式中、ｐ＝４、ｍ＝１または２、およびｔ＝１〜３であり、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１は、 水素、ハロゲン（フッ素、塩素、臭素およびヨウ素）、アルキル、ハロゲン化アルキルなどの置換アルキル、ニトロ、シアノ、チオアルキル、アルコキシ、ハロゲン化アルコキシなどの置換アルコキシ、アリールまたはハロゲン化アリールなどの置換アリール、アルキルエステルおよび置換アルキルエステルならびにこれらの組合せから成る群から選択される。Ｒ_６はそれぞれ異なってもよく、Ｒ_７はそれぞれ異なってもよく、Ｒ_８はそれぞれ異なってもよく、Ｒ_９はそれぞれ異なってもよく、Ｒ_１０はそれぞれ異なってもよく、Ｒ_１１はそれぞれ異なってもよいことを理解されるべきである。Ｇ_２およびＧ_３は共有結合；ＣＨ_２基；Ｃ（ＣＨ_３）_２基；Ｃ（ＣＦ_３）_２基；Ｃ（ＣＸ_３）_２基から成る群から選択され、Ｘはハロゲン；ＣＯ基；Ｏ原子；Ｓ原子；ＳＯ_２基；Ｓｉ（ＣＨ_３）_２基；９，９−フルオレン基；置換９，９−フルオレン；およびＯＺＯ基であり、Ｚはアリール基またはフェニル基、ビフェニル基、パーフルオロビフェニル基、９，９−ビスフェニルフルオレン基、および置換９，９−ビスフェニルフルオレンなどの置換アリール基である。 And two or more aromatic diamines represented by the following general structure:

In the above formulae, p = 4, m = 1 or 2, and t = 1 to 3, R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ is hydrogen, halogen (fluorine, chlorine , Bromine and iodine), alkyl, substituted alkyl such as halogenated alkyl, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy such as halogenated alkoxy, substituted aryl such as aryl or halogenated aryl, alkyl ester and substituted alkyl ester, and these Are selected from the group consisting of combinations of R ₆ may be different, R ₇ may be different, R ₈ may be different, R ₉ may be different, R ₁₀ may be different, R ₁₁ may be different It should be understood that it may. G ₂ and _{G 3} are covalent bonds; is selected from the group consisting of C _{(CX 3) 2} group, X is a halogen;; CH ₂ group; C _{(CH 3) 2} group; C _{(CF 3) 2} group CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9,9-fluorene; a and OZO group, Z is an aryl group or a phenyl group, a biphenyl group, PA A fluoroaryl group, a 9,9-bisphenyl fluorene group, and a substituted aryl group such as a substituted 9,9-bisphenyl fluorene group.

  The present invention relates to transparent films prepared from aromatic copolyamides. The polyamide is prepared in a solvent via condensation polymerization, and the hydrochloric acid produced in this reaction is captured by a reagent such as propylene oxide (PrO). The film can be produced directly from the reaction mixture without needing to isolate and re-dissolve the polyamide. Colorless films can be prepared by direct casting procedures from the polymerization solution. The product of the reaction of hydrochloric acid with PrO is removed upon removal of the solvent. These films exhibit low CTE when cast and do not need to be stretched. By carefully manipulating the proportions of the monomers used to prepare the copolyamides, it is possible to control the CTE and Tg of the resulting copolymers and the optical properties of their solution cast films. It is particularly surprising that the film becomes curable at high temperatures when free carboxylic acid side chains are present on the polymer chain. If the reaction of the reagent with hydrochloric acid does not form a volatile product, the polymer is isolated from the polymerization mixture by precipitation, redissolved with a polar solvent (without the need for inorganic salts) and cast into a film . If the reaction of the reagents with hydrochloric acid forms a volatile product, the film can be cast directly. One example of the above-described reagent that forms a volatile product is PrO.

イソフタロイルジクロリド（ＩＰＣ）；

２，６−ナフタロイルジクロリド（ＮＤＣ）；

４，４’− ビフェニルジカルボニルジクロリド（ＢＰＤＣ）

Representative and illustrative examples of useful aromatic diacid dichlorides of the present invention include:
Terephthaloyl dichloride (TPC);

Isophthaloyl dichloride (IPC);

2,6-Naphthaloyl dichloride (NDC);

4,4'-biphenyl dicarbonyl dichloride (BPDC)

９，９−ビス（４−アミノフェニル）フルオリン（ＦＤＡ）

９，９−ビス（３−フルオロ−４−アミノフェニル）フルオリン（ＦＦＤＡ）

４，４’−ジアミノジフェン酸 （ＤＡＤＰ）

３，５−ジアミノ安息香酸 （ＤＡＢ）

４，４’−ジアミノ−２，２’− ビストリフルメトキシルベンジジン（ＰＦＭＯＢ）

４，４’−ジアミノ−２，２’−ビストリフルオロメチルジフェニルエーテル（６ＦＯＤＡ）

ビス（４−アミノ−２−トリフルオロメチルフェニルオキシル）ベンゼン（６ＦＯＱＤＡ）

ビス（４−アミノ−２−トリフルオメチルフェニルオキシル）ビフェニル（６ＦＯＢＤＡ）

Representative and illustrative examples of useful aromatic diamines of the present invention include:
4,4'-Diamino-2,2'-bistrifluoromethylbenzidine (PFMB)

9,9-Bis (4-aminophenyl) fluorin (FDA)

9,9-Bis (3-fluoro-4-aminophenyl) fluorin (FFDA)

4,4'-Diaminodiphenic acid (DADP)

3,5-diaminobenzoic acid (DAB)

4,4'-Diamino-2,2'-bistrifluoromethoxybenzidine (PFMOB)

4,4'-Diamino-2,2'-bistrifluoromethyl diphenyl ether (6 FODA)

Bis (4-amino-2-trifluoromethylphenyloxyl) benzene (6FOQDA)

Bis (4-amino-2-trifluoromethylphenyloxyl) biphenyl (6FOBDA)

  Example 1. This example describes the general procedure for the preparation of copolymers from TPC, IPC and PFMB (70% / 30% / 100% moles) by solution condensation.

  PFMB (3.2024 g, 0.01 mol) and dried DMAc (45 ml) are added to a 250 ml 3-neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet and outlet. After PFMB is completely dissolved, IPC (0.6395 g, 0.003 mol) is added to the solution under nitrogen at room temperature and the flask wall is washed with DMAc (1.5 ml). After 15 minutes, TPC (1.4211 g, 0.007 mol) is added to the solution and the flask wall is again washed with DMAc (1.5 ml). The viscosity of the solution increases until the mixture forms a gel. After adding PrO (1.4 g, 0.024 mol), the gel is stirred and crushed to form a viscous, homogeneous solution. After stirring for an additional 4 hours at room temperature, the resulting copolymer solution can be cast and formed directly into a film.

  Example 2. This example describes the general procedure for the preparation of copolymers from TPC, PFMB and FDA (100% / 80% / 20% moles) by solution condensation.

  PFMB (1.0247 g, 3.2 mmol), FDA (0.02 788 g, 0.8 mmol) and dried DMAc (20 ml) in a 100 ml four-necked round bottom flask equipped with a mechanical stirrer, nitrogen inlet and outlet ) At room temperature under nitrogen. After PFMB is completely dissolved, TPC (0.8201 g, 4.04 mmol) is added to the solution and the flask wall is washed with DMAc (5.0 ml). The viscosity of the solution increases until the mixture forms a gel. After adding PrO (0.5 g, 8.5 mmol), the gel is stirred and ground to form a viscous, homogeneous solution. After stirring for an additional 4 hours at room temperature, the resulting copolymer solution can be cast and formed directly into a film.

  Example 3. This example describes the general procedure for the preparation of copolymers from TPC, IPC, DADP and PFMB (70% / 30% / 3% / 97% moles) by solution condensation.

  PFMB (3.1060 g, 0.0097 mol), DADP (0.0817 g, 0.0003 mol) and dried DMAc (45 ml) in a 250 ml 3-neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet and outlet ) At room temperature under nitrogen. After PFMB is completely dissolved, add IPC (0.6091 g, 0.003 mol) to the solution and wash the flask wall with DMAc (1.5 ml). After 15 minutes, TPC (1.4211 g, 0.007 mol) is added to the solution and the flask wall is again washed with DMAc (1.5 ml). The viscosity of the solution increases until the mixture forms a gel. After adding PrO (1.4 g, 0.024 mol), the gel is stirred and crushed to form a viscous, homogeneous solution. After stirring for an additional 4 hours at room temperature, the resulting copolymer solution can be cast and formed directly into a film.

  Example 4. This example describes the general procedure for the preparation of copolymers from TPC, IPC, DAB and PFMB (75% / 25% / 5% / 95% moles) by solution condensation.

  PFMB (3.0423 g, 0.0095 mol), DAB (0.0761 g, 0.0005 mol) and dried DMAc (45 ml) in a 250 ml 3-neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet and outlet ) At room temperature under nitrogen. After PFMB is completely dissolved, add IPC (0.5076 g, 0.0025 mol) to the solution and wash the flask wall with DMAc (1.5 ml). After 15 minutes, TPC (1.5227 g, 0.0075 mol) is added and the flask wall is again washed with DMAc (1.5 ml). The viscosity of the solution increases until the mixture forms a gel. After adding PrO (1.4 g, 0.024 mol), the gel is stirred and crushed to form a viscous, homogeneous solution. After stirring for an additional 4 hours at room temperature, the resulting copolymer solution can be cast and formed directly into a film.

  Although the temperature described in the above examples is room temperature, the temperature range can be from about -20 ° C to about 50 ° C, and in some embodiments, from about 0 ° C to about 30 ° C. Should be understood.

Preparation and Characterization of Polymeric Films The polymer solution can be used directly for the film after polymerization. For small film preparation in a batch process, the solution is poured onto a flat glass plate or other substrate and the film thickness is adjusted by a doctor blade. After drying for several hours at 60 ° C. under reduced pressure on the substrate, the film is dried at 200 ° C. for a further hour under the protection of a dry nitrogen stream. The film is cured by heating at or near the polymer Tg for a few minutes under vacuum or in an inert atmosphere. Mechanical removal from the substrate results in a free-standing film having a thickness greater than about 10 μm. The thickness of the free standing film can be adjusted by adjusting the solids content and viscosity of the polymer solution. It should be understood that the film can be cured at any temperature from about 90% to about 110% of the Tg. It is also understood that the batch process can be modified to be able to be carried out continuously in a roll-to-roll process by techniques known to those skilled in the art.

  In one embodiment of the invention, the polymer solution can be solution cast onto a reinforced substrate such as thin glass, silica or microelectronics. In this case, the process is adjusted so that the final polyamide film thickness exceeds about 5 μm.

  CTE and Tg are measured using a thermomechanical analyzer (TA Q 400 TMA). The sample film has a thickness of about 20 μm and a load strain of 0.05 N. In one embodiment, the thickness of the free-standing film is about 20 μm to about 125 μm. In one embodiment, the film is attached to a reinforced substrate, and the film thickness is <20 μm. In one embodiment, it is understood that the CTE is less than about 20 ppm / ° C., while in other embodiments the CTE is less than about 15 ppm / ° C., less than about 10 ppm / ° C., and less than about 5 ppm / ° C. ing. In these embodiments, the CTE can be less than about 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6 or 5 ppm / ° C. Should be understood. The experimentally derived CTE is an average of CTE determined between room temperature and about 250 ° C.

  Film transparency is measured by determining the light transmission of a 10 μm thick film at 400-750 nm using a UV-visible spectrophotometer (Shimadzu UV-2450).

  The solvent resistance of the film is measured by immersing the film in the selected solvent for 30 minutes at room temperature. The film is considered to be solvent resistant after immersion, substantially without surface wrinkles, swelling or other visible damage. Solvent resistant films are useful as substrates for flexible electronic devices.

  To determine the proportion of reactants necessary to obtain a soluble copolyamide that can be solution cast onto a colorless film with a Tg> 300 ° C., CTE <20 ppm and a light transmittance> 80% at 400-750 nm Preliminary studies can be carried out by systematically varying the amount of reactants free of free carboxyl groups. In order to determine suitable copolymer candidates (base polymers) for the incorporation of free carboxyl groups, the properties of the film of the resulting copolymer are measured. Such studies are well understood by those skilled in the art. The following table shows a comparative example of that type of study used to determine some of the base polymers utilized in the present invention.

  In order to determine the minimum amount of carboxyl groups required to thermally crosslink the copolymer without significantly changing the properties, various amounts of reactants containing free carboxyl groups are used as the basis of the resulting copolymer A second preliminary study can be carried out to copolymerize with the mixture of reactants used to prepare the polymeric film to determine their properties. For example, various amounts of DADP were copolymerized with the reactants used to prepare the base polymer made from a mixture of TPC, IPC and PFMB (Example 1) in a ratio of 70/30/100. The resulting copolymer film containing DADP was heat treated at 330 ° C. for 5 minutes. After curing, the resistance of the film to NMP was evaluated. The results are shown in Table 3.

  The properties of the polymeric film according to Example 3 after curing are shown in Table 4. The composition of the copolymer containing DAB (Example 4) was determined in the same manner and is shown in Table 4 together with the properties of the cured film of this polymer.

  The cured film of the present invention is resistant to both inorganic solvents and organic solvents. The solvent resistance of the film can be quickly evaluated by analyzing the resistance to NMP, a commonly used strong solvent. It has been found that films resistant to this solvent are also resistant to other polar solvents.

  The following are exemplary polymers that can be used in the present invention: 1) about 50 to 70 mol% TPC, about 30 to about 50 mol% IPC, about 90 to about 99 mol% PFMB, and About 1 to about 10 mole% 4,4'-diaminodiphenic acid (DADP); 2) about 50 to about 70 mole% TPC, about 25 to about 50 mole% IPC, about 90 to about 96 mole% PFMB, and about 4 to about 10 mole% 3,5-diaminobenzoic acid (DAB); 3) about 100 mole% TPC, about 25 to about 85 mole% PFMB, about 15 to about 50 mole% 9,9-bis (4-aminophenyl) fluorin (FDA), and about 1 to about 10 mole% DADP; and 4) about 100 mole% TPC, about 50 to about 85 mole% PFMB, about 15 to about 5 mole% About 50 mole% of the FDA, and About 4 to about 10 mole percent of the DAB.

  The embodiment has been described above. It will be apparent to those skilled in the art that the methods and apparatus described above can incorporate changes and modifications without departing from the general scope of the invention. All such changes and modifications are intended to be included as long as within the scope of the appended claims or the equivalents thereof. Although the above description contains many specificities, it should not be construed as limiting the scope of the invention, but merely as being illustrative of some of the embodiments of the invention. Various other embodiments and derivations are possible within the scope.

  Furthermore, although the numerical ranges and parameters defining the broad scope of the present invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains an error which necessarily results from the standard deviation present in each test measurement.

Claims (17)

Glass transition temperature of greater than 3 00 ° C., and a process for the thermal expansion coefficient to produce less than 2 0 ppm / ° C., the thermal and dimensional stable transparent aromatic copolyamide films, the following steps:
a) forming a mixture of aromatic diamines, wherein the mixture comprises at least one first aromatic diamine and one second aromatic diamine, the amount of the second aromatic diamine There exceed 1 mole% of the total aromatic diamine mixture, as do one 1 is less than 0 mol%, the second aromatic diamine is possible to free carboxylic acid groups to include one or more;
b) dissolving the aromatic diamine mixture in a polar solvent;
c) reacting the diamine mixture with at least one aromatic diacid dichloride to form hydrochloric acid and a polyamide solution;
d) removing the hydrochloric acid using a reagent;
e) casting the polyamide solution to form a film; and f) curing the film at a temperature at which the film becomes solvent resistant by thermal crosslinking,
A process characterized in that the film is produced in the absence of inorganic salts. The second aromatic diamine has a general formula:

In which n = 1 to 4 and Ar is a group comprising:

And n is 1 or 2, t is 1 to 3 and R ₉ , R ₁₀ and R ₁₁ are hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano, thioalkyl, G ₃ is selected from the group comprising alkoxy, substituted alkoxy, aryl, substituted aryl, alkyl esters, substituted alkyl esters, and combinations thereof, G ₃ is a covalent bond; a CH ₂ group; a C (CH ₃ ) ₂ group; _{3) 2} group; C _{(CX 3)} is selected from the group comprising ₂ group, X is a halogen; CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} group; 9,9-fluorene And Z is an aryl group, or a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group, and Characterized in that from the group consisting of conversion of 9,9-bis-phenyl fluorene substituted aryl group selected, the process according to claim 1.   Process according to claim 2, characterized in that the second aromatic diamine is 4,4'-diaminodiphenic acid or 3,5-diaminobenzoic acid.   The first aromatic diamine is 4,4'-diamino-2,2'-bistrifluoromethylbenzidine, 9,9-bis (4-aminophenyl) fluorin, and 9,9-bis (3-fluoro- 4-aminophenyl) fluorin, 4,4'-diamino-2,2'-bistrifluoromethoxybenzidine, 4,4'-diamino-2,2'-bistrifluoromethyldiphenyl ether, bis- (4-amino-2-) Process according to claim 1, characterized in that it is selected from the group comprising trifluoromethylphenyloxyl) benzene and bis- (4-amino-2-trifluoromethylphenyloxyl) biphenyl.   The process according to claim 1, characterized in that the polar solvent is an inorganic solvent.   Process according to claim 1, characterized in that the polar solvent is N, N-dimethylacetamide or N-methyl-2-pyrrolidinone.   The at least one aromatic diacid dichloride is selected from the group comprising terephthaloyl dichloride, isophthaloyl dichloride, 2,6-naphthaloyl dichloride and 4,4-biphenyl dicarbonyl dichloride The process according to claim 1, wherein   A process according to claim 1, characterized in that the film is produced in the absence of inorganic salts and is insoluble in organic solvents.   The process of claim 1, wherein said casting step comprises casting the resulting polyamide solution onto a free standing film or reinforced substrate.   The process of claim 1 wherein the curing temperature is at least 300 ° C and the film is cured for at least 5 minutes. Characterized in that it consists of thermally crosslinked aromatic copolyamide, characterized by the following general formula (I) and at least two repeating units of (II), a transparent film having a glass transition temperature greater than 3 00 ° C. :

(In the above formula, n = 1 to 3;
The ratio of X to Y is chosen such that the copolyamide is soluble in polar aprotic solvents and can be solution cast onto a transparent film having a coefficient of thermal expansion of less than 20 ppm / ° C .;
Ar ₁ is selected from the group comprising:

In the above formula, p = 4 and q = 3, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy , Aryl or substituted aryl, alkyl ester, substituted alkyl ester, and combinations thereof, wherein G ₁ is a covalent bond; CH ₂ group; C (CH ₃ ) ₂ group; C (CF ₃ ) ₂ group ; C is selected from the group comprising _{(CX 3) 2} group, X is a halogen; CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9 And OZO group, Z is an aryl group, or a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group, and a substituted 9,9-bisphenyl group. A substituted aryl group selected from the group consisting of nil fluorene;
Ar ₂ is selected from the group comprising:

In the above formula, p = 4, and R ₆ , R ₇ and R ₈ are hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, alkyl ester and substituted alkyl esters, and is selected from the group comprising a combination thereof, _{G 2} is a covalent bond; comprising a C _{(CX 3) 2} group; CH ₂ group; C _{(CH 3) 2} group; C _{(CF 3) 2} group Group X; halogen; CO group; O atom; S atom; SO ₂ group; Si (CH ₃ ) ₂ group; 9,9-fluorene group; substituted 9,9-fluorene; and OZO group And Z each represents an aryl group, or a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenylfluorene group, and a substituted 9,9-bisphenylfluorene group. A substituted aryl group selected from the group,
Ar ₃ is selected from the group comprising:

In the above-mentioned formula, m is 1 or 2, t is 1 to 3, and R ₉ , R ₁₀ and R ₁₁ are hydrogen, halogen, alkyl, substituted alkyl, nitro, cyano, thioalkyl, alkoxy, substituted alkoxy , Aryl, substituted aryl, alkyl ester, substituted alkyl ester, and combinations thereof, wherein G ₃ is a covalent bond; CH ₂ group; C (CH ₃ ) ₂ group; C (CF ₃ ) ₂ group ; C is selected from the group comprising _{(CX 3) 2} group, X is a halogen; CO group; O atom; S atoms; SO ₂ group; Si _{(CH 3) 2} groups; 9,9-fluorene group, a substituted 9 And OZO group, Z is an aryl group, or a phenyl group, a biphenyl group, a perfluorobiphenyl group, a 9,9-bisphenyl fluorene group, and a substituted 9,9-biphenyl group. A substituted aryl group selected from the group consisting of phenyl fluorene, if t is less than 3, the remaining positions of the aromatic ring are hydrogen atoms).   In the formula (I), X is a molar ratio of the repeating structure (I), is 0.90 to 0.99, Y is a molar ratio of the repeating structure (II), 0.01 to 0.10 The transparent film according to claim 11, characterized in that The aromatic copolyamide according to claim 11, characterized in that it comprises a plurality of repeat units having the structures (I) and (II) in which Ar ₁ , Ar ₂ and Ar ₃ are identical or different. Transparent film. The transparent film according to claim 1 or 11, characterized in that the thickness of the film is more than 20 μm and the transparency is more than 80% at 400 to 750 nm. The transparent film according to claim 1 , wherein the film has a thickness of 5 μm to 100 μm. Characterized in that curing the film at a temperature of between 90% and 1 10% of the glass transition temperature of the film, a transparent film according to claim 1 or 11. The transparent film according to claim 1 , wherein the film has a thermal expansion coefficient of less than 10 ppm / ° C.